CN104822745B

CN104822745B - Phenolic foams

Info

Publication number: CN104822745B
Application number: CN201380054900.8A
Authority: CN
Inventors: M·罗什福尔; L·里普利; P·奥兰; V·科波克
Original assignee: Kingspan Holdings IRL Ltd
Current assignee: Kingspan Holdings IRL Ltd
Priority date: 2012-09-18
Filing date: 2013-09-18
Publication date: 2018-03-13
Anticipated expiration: 2033-09-18
Also published as: CN104822745A; AU2013320300A1; JP2015529269A; GB201223270D0; JP6300041B2; NZ706641A; CA2885123A1; EP2898005A1; GB2505974A; US20150225528A1; US9896559B2; SG11201502041TA; AU2013320300B2; CA2885123C; WO2014044715A1; DK2898005T3; GB2505974B; EP2898005B1

Abstract

The present invention relates to phenolic aldehyde closed-cell foam, and it includes hydrocarbon blowing agent and at least 1 weight % alkali silicate.According to EN 13166:The aged thermal conductivity that 2008 method measures the foams is less than 0.025W/m.K.The foams are formed by the resol mixture that water content is more than 15 weight % but is less than 24 weight %.

Description

Phenolic foams

Technical field

The present invention relates to phenolic foams.

Background technology

In history, under case of fire low smog emission and can self-extinguishment ability when being of crucial importance, phenolic resin has turned into Preferable thermoset resin material.Applied in building, heating, ventilation and pipe insulation, wherein phenolic foams provides heat-insulated Property and fire resistance.

At present, in the manufacture of phenolic cellular foam, phenolic resin such as resol is generally by having by force Machine acid or strong inorganic acid are catalyzed.For example, EP0170357A describes a kind of preparation method of acid cured phenolic resin foams. The selection of sour species depends on required hardening time and temperature.Produced when the foaming agent being mixed into resin comes to life Raw porous heat-insulating foams.Hydrocarbon or its mixture are conventional foaming agents.Temperature range at 15 DEG C -70 DEG C generally occurs for expansion It is interior.Need to take care in phenolic foams is manufactured to ensure to produce the excessive exotherms of resin.If the resin system prepared In total water percentage composition it is too low, such as be easier when using strong acid as catalyst uncontrollable exothermic chemical occurs anti- Should.When exothermic reaction occurs, water or steam are produced by the polycondensation reaction of phenolic resin in addition.This is to forming closed-cell foam Ability adversely affect.Similarly, if selected phenolic resin has too high water content, closed pore bubble will not be produced Foam body.It is highly desirable to obtain the structure of closed-cell foam so that heat-proof quality maximizes.By start solidification and foaming agent it Before, the water percentage composition of uncured phenolic resin system is controlled, and solidify at high temperature, it can be made with hole-closing structure Phenolic resin foam.Also need to select the species and use of each phenolic resin, acid catalyst, surfactant and foaming agent Amount, for mixing and being cured to obtain preferable closed-cell foam at high temperature.

It can verify whether the abscess of foams has defect such as eyelet or crack using electron microscope.Preferably It is to have low-density, flawless closed-cell foam heat-insulated for stablizing for low cost.The defects of hole may cause chemical hair Infusion is lost in from hole and air is diffused into hole, causes thermal conductivity to raise.This is undesirable for heat-barrier material.

Particularly, it is desirable to provide the closed cell phenolic foam of the low-density without eyelet or crack on abscess.Furthermore, it is necessary to One kind can at moderate temperatures (10-30 DEG C) hold miscible phenolic resin system.Commercially consider preferably in the mill to hold Miscible low viscosity resin system.

Phenolic foams can be prepared into the moulding part of blocks, laminate or given shape.In a kind of commercial run, Produce typical thickness and 25-60kg/m with 20mm-150mm³Dry density lamination phenol formaldehyde foam thermal insulation board.In the party In method, traditional high shear or high pressure top-type mixer mixing phenolic resin, acid and foaming agent are used.Then will be catalyzed Liquid resin is added in foam laminating machine and carried out between aluminium foil, steel plate, paper or glass gasket.Then start to foam With solidify and make resin solidification formed froth pulp.Generally these froth pulps are made in about 2-15 minutes at 50-80 DEG C, and it is wrapped Include such as thermal insulation board.Then it is generally necessary to which the froth pulp is further solidified, generally quilt is generally for example passed through at high temperature Baking oven " solidify afterwards " referred to as, such as the 1-72 hours at 50-90 DEG C, to produce enough processing intensity.The resin system The chemical composition with typical weight ratio being listed below is generally included, in parts by weight (pbw)：

Liquid resol containing 1-10% surfactants (usual 60-85% solidifies solid)：100pbw

Foaming agent (be usually hydrocarbon and/or based on hydrocarbon)：4-20pbw

Organic acid or inorganic acid：9-30pbw.

When manufacturing phenolic foam products such as thermal insulation board first, the thermal conductivity (λ value) at 23 DEG C is usually 0.017- 0.024W/m.K, depending on selected foaming agent.The characteristics of so low heat conductivity value is the hole-closing structure of reservation foaming agent, Therefore substantially few abscess defects are shown.Cell size is usually 30-200 μm.In order to effectively heat-insulated, it is necessary to froth pulp There is long-term low thermal conductivity stability (λ value) including laminated foam product such as plate.In order to prove at room temperature long-term low Thermal conductivity stability, can be by the sample of froth pulp such as plate according to European standard EN 13166：2008 (or EN14314： 2009) method carries out prolonging prolonged heat ageing at such as 70 DEG C -110 DEG C.If λ value is low simultaneously after the acceleration heat ageing And stably, then it can reasonably think to show that such low and stability number froth pulp such as thermal insulation board will provide in use Long-term lower thermal conductivity.

In the manufacture of the phenolic foams of acid solidification, if to obtain hole-closing structure, it must be carefully controlled and used Manufacturing condition.It is 25-60kg/m for density if not observing strict production routine³Foams initial lambda values may Up to 0.030-0.040W/m.K；This shows that the integrality of closed pore has been lost and air enters in abscess.In phenolic foams Manufacture used in catalyst species and dosage have significant impact to the long-time stability of abscess.Increase acid catalyst It is horizontal easily to produce the foams with high initial lambda values, and/or λ value unacceptable elevated foams over time.

Requirement to heat-insulated phenolic foams in building industry is not only to show good initial thermal conductivity properties, and And these properties are also kept when aging.This means when initial installation the product not only to show it is good heat-insulated Performance and in validity period, this has been probably decades, also to show relatively good heat-proof quality.

Have been carried out many trials that foams are assigned with good aging thermal insulation.It is various that these trials include addition Surfactant adds plasticizer to assign foams pliability so as to avoid to improve the foaming of foams and foam stability Foam Interior cracking, using different types of filler, change the foaming agent used, change method parameter such as temperature and catalysis Degree.Nevertheless, these are used for the commercially available phenol formaldehyde foam that construction market, heating and ventilatory applications and industrial purpose are sold Body does not show good long-term holding thermal conductivity.

On the other hand other properties of foams or the resin for forming foams have been described.Such as UK patents GB1351476 solves many problems.It first relates to the physical property of uncured resin and particularly prepared flowable Resin combination makes them to be easily pumped in the cavity between wall simultaneously in-situ solidifying.It is said that filler is hindered in foam inflow In absolutely empty.In order to solve the problem, aqueous expandable phenol resin composition is prepared, it includes phenol-aldehyde condensate, particle Mineral filler, " waterglass " and swelling agent.The patent, which is related to provide, shows that the resin with good flowability makes the resin can The resin of space and offer with nonflammable property being added between cavity wall.Therefore its teaching is that formulation on the one hand can not With too many filler in order to meet flowable, any reduction of filler is on the other hand made up, because reducing the dosage of filler The inflammability of material to being formed by composition has adverse effect.

" waterglass " is defined as sodium metasilicate and/or potassium silicate in the patent in question." embodiment " and " contrast test " seemingly Display waterglass content has " unexpected effect " to improving fire resistance.Therefore waterglass is used as replacing in composition For the water base inert filler of granular filler, to be obtained between the mobility of resin and the inflammability of caused solidification foams Balance.

The present invention relates to it is different the problem of, that is, realize lower thermal conductivity, particularly realize that the lower thermal conductivity of long-term ageing (such as exists EN 13166：2008 or EN14314：Defined in 2009).

French Patent (FRP) publication FR 2,157,674, which describes, adds sodium metasilicate into phenol.The sodium metasilicate is in soda acid As the consumption of sodium metasilicate makes phenol deprotonation in reaction.

US 2003/0216847 describes a kind of closed-cell foam as made from new crosslinked phenolic epoxy resin, with On as the GB 1351476 that is discussed, wherein adding sodium metasilicate as fire proofing.

The content of the invention

The present invention provides a kind of phenolic foams, and it includes：

Phenolic resin such as resol,

Catalyst such as acid catalyst,

Foaming agent such as hydrocarbon, and including

At least 1 weight % alkali silicate of the foams；

According to EN 13166：The aged thermal conductivity that 2008 method measures the foams is less than 0.025W/m.K.

Offer shows that the froth pulp of so low aged thermal conductivity's value is beneficial.It is considered herein that it may also provide root According to EN 13166：2008 or EN 14314：2009 method measures the froth pulp that aged thermal conductivity is less than 0.020W/m.K.

The percetage by weight of silicate in the resin mixture, compared with the amount in foams, without any substantive journey The change of degree.Any difference in the drying process of foams mainly due to caused by losing some moisture.

The closed pore that suitable surfactant can be used to ensure is formed and integrality.Suitable surfactant includes Selected from the following group those：APES, triglyceride ethoxylate and particular silicone and they Combination.The surfactant preferably exists with the 2-7 weight % of foams amount.

The froth pulp of formation will not largely lose its expanded form.Such as froth pulp will be certainly after its formation Vertical.Have found using composition such as those compositions from GB 1351476 not for example using the foam of the present invention The preferable hole-closing structure that body is realized.

In addition, there is the froth pulp of the present invention enough structural intergrities make it that they are after initial solidification and any (secondary solidification can for example be carried out by heating) is easily handled before secondary solidification.They are typically not flowable to have solid Denseness.Compare, it has been found that there is no enough processing intensity to make it can be in any way by the products formed of GB 1351476 Handle for being processed further.In many applications of the froth pulp of the present invention, they must have enough hardness to make it Required shape can be made into.Such as they can be made into the c- types section of plate, panel, bending sections for example for pipe insulation Deng.

It is preferred that forming the foams by phenolic resin blend, the water content of the phenolic resin blend mixes for resin About 12 about 24 weight % of weight %-24 weight %, e.g., from about 13- of compound, e.g., from about 15-24 weight %, are suitably about 15%-21 weight %.

The water of the amount can be used in phenolic resin such as resol, to react the phase in the processing of foams Between reduce viscosity be easy to the processing of liquid and promote to mix.But even if using above-mentioned total water content, despite the fact that the water Content may generally produce adverse effect to aged thermal conductivity, but froth pulp provided by the invention show it is ideal old Change thermal conductivity.

By contrast, GB 1351476 is described using the phenolic resin system of high percentage water content to prepare phenol formaldehyde foam The embodiment of body.Describe to use in the embodiment of the 88-110 rows of page 2 of GB 1351476 and there is 27%-30% water contents Phenolic resin.In addition, used acid catalyst is 50% aqueous solution of toluenesulfonic acid, total water of resin system is added into In content.The sodium silicate aqueous solution (sodium silicate) that GB 1351476 also describes addition 45-50% is resistance to improve as auxiliary agent Fiery performance.It is clear to the skilled person that the aqueous solution of acid and sodium silicate aqueous solution will be added into phenolic resin entirely to match somebody with somebody Total water content of resin system processed is improved to 36.3 weight %-38.3 weight %, the preparation resin system include phenolic resin, Alkali silicate, foaming agent and acid catalyst.In this computation, filler such as vermiculite filler is left out.The knot By being based on calculating total water content before solidification and foaming in the description of this document page 2 87-102 rows.

For the purposes of the present invention, when calculating existing water percetage by weight, in order to calculate ignored unique group It is existing any filler to divide.What filler was optionally present, but even if in the presence of they are also arranged from the calculating of water percentage amounts Remove.In order to omparison purpose, such as compared with GB 1351476, according to identical basis, i.e., do not include filler, to be counted Calculate.

As shown in present inventor, led to using the resol of high water content and/or the acid of high water content Can often produce has the foam cell structure of excessive eyelet on hole wall.These eyelets are largely easy to use electron microscope (SEM) observe.Eyelet on hole wall causes the loss with time foaming agent, and this causes to produce relatively high long-term thermal conductivity Rate, more than 0.025W/m.K, and usually more than 0.030W/m.K.

Using the alkali silicate of sufficient amount to assign preferable aged thermal conductivity.

The alkali silicate can exist with 1 weight %-10 weight % of phenolic foams amount.

In some embodiments, the alkali silicate is with 2.5 weight %-5 weight % of phenolic foams amount In the presence of.

The alkali silicate can be hydrated, formula A₂SiO₃·nH₂O, wherein A are the 1st of the periodic table of elements The alkali metal and n of main group are 1-9 integer.

In some embodiments, one kind in sodium metasilicate, potassium silicate and lithium metasilicate of the alkali silicate or It is a variety of.

In one case, the silicate is sodium metasilicate pentahydrate.In another case, the silicate is silicon Sour potassium.In still another case, the silicate is lithium metasilicate.

The hydrocarbon may include the mixture of hydrocarbon.

In one embodiment, the hydrocarbon blowing agent includes at least one pentane.

The hydrocarbon may include the mixture of pentamethylene and isopentane.

In another case, the hydrocarbon includes the mixture of isopropyl chloride and isopentane.

In some embodiments, the hydrocarbon includes perfluoro alkane.

In a particularly preferred embodiment of the present invention, formed by acid catalyzed resol mixture Foams, the resol mixture include surfactant and foaming agent, and its water content is about 15 weight %-24 Weight %, it is greater than 15 weight % but is less than 24 weight %, and (does not consider the filler being optionally present in the mixture In the case of) alkali silicate be present and cause the foams as made from the mixture to include at least 1 weight % alkali metal Silicate.

In one case, alkali silicate be present in acid catalyzed resol mixture to cause then Obtained foams contain 1 weight %-10 weight % alkali silicate.

In some embodiments, alkali silicate be present in acid catalyzed resol mixture to cause Then obtained foams contain and (do not consider filler) 2.5 weight %-5 weight % alkali silicate.

Surprisingly it has been found that after heat ageing is accelerated, can be made with stable low less than 0.025W/m.K The closed cell phenolic foam of the hydrocarbon foaming of thermal conductivity.Foams, the preparation phenolic aldehyde tree are prepared using formulated phenolic resin system Resin system includes resol, surfactant, acid catalyst, alkali silicate, foaming agent and is optionally present Filler.The water content of the formulated phenolic resin system is 15%-24%.By alkali silicate, particularly sodium metasilicate, potassium silicate Or lithium metasilicate is generally added to phenolic resin according to the ratio of the resol of every 100 parts by weight of 1.0-5.0 parts by weight In.Aged thermal conductivity the ＞ 0.025W/m.K, usual ＞ 0.03W/ for this foams being modified in the absence of alkali silicate m.K。

Liquid or gas foaming (such as hydrocarbon foaming) in the phenolic foams as made from high water phenolic resin/acid system Foams hole wall in small pin hole allow at high temperature such as 110 DEG C foaming agent during aging 2 weeks to be moved from foams Removal is gone.We have surprisingly found that added in the manufacturing process of foams the sodium metasilicate of liquid form or solid form, Potassium silicate or lithium metasilicate seem that it is considered as the thin film of silica dioxide gel to produce, and the film covers most of foam body acupuncture Hole, therefore retain more foaming agents.It is achieved thereby that improve aged thermal conductivity's (λ value) of (lower).

The present invention provides a kind of method, and methods described is the first stage phenolic prepared by using suitable modification of foaming agent Resin there is no the closed-cell foam of perforate eyelet to manufacture on hole wall, and this method, which makes it possible to easily be made, to be had The foams of long-term low thermal conductivity, the resol of the preparation include surfactant, foaming agent, acid catalyst and Alkali silicate, but its water content is 15 weight %-24 weight % in the case of the filler for not considering to be optionally present.

Viscosity of the resin at 25 DEG C is usually 1000-12000cps, preferably 2000-9000cps.

The method that the present invention provides a kind of froth pulp of manufacture with good (low) thermal conductivity, methods described include by Composition forms foams to manufacture closed-cell foam product, and the composition includes：

(first stage) phenolic resin mixing comprising surfactant, (acid) catalyst, foaming agent and alkali silicate Thing, and

The filler being optionally present；

For the weight % of about 15 weight %- about 24 of composition, (wherein described water content is base to the water content of the composition The weight of composition in the case of existing any filler is not considered).

This method uses suitable foaming agent to cause the bore closure in the hole wall of foams, so as to easily be made Foams with long-term low thermal conductivity.It has been found that the hole in the substantially seldom defective such as hole of the froth pulp formed Eye, therefore compared with the froth pulp as made from analogous composition, there is obvious preferably (lower) thermal conductivity.

The invention further relates to a kind of method for manufacturing froth pulp, methods described includes providing a kind of composition, and solidifies Foams are to manufacture closed-cell foam product, according to EN 13166：2008 method measures the aged thermal conductivity of the froth pulp Less than 0.025W/m.K, wherein the composition includes：Phenolic resin, catalyst, foaming agent, surfactant and alkali metal silicon Hydrochlorate, and the filler being optionally present.

The present invention also provides alkali silicate and is used to manufacture closed pore as the additive in phenol formaldehyde foam resin combination The purposes of froth pulp, according to EN 13166：The aged thermal conductivity that 2008 method measures the closed-cell foam product is less than 0.025W/m.K。

The present invention also provides a kind of resin compound for being used to form phenolic foams, and the resin compound includes alkali gold Belong to silicate, particularly sodium metasilicate, potassium silicate or lithium metasilicate or combinations thereof.Also provide a kind of for forming phenolic foams Resin compound, the resin compound includes (first stage) phenolic resin system, (first stage) phenolic resin system Including surfactant, (acid) catalyst, foaming agent and alkali silicate, but in the feelings for the filler for not considering to be optionally present The water content of the resin compound is 15 weight %-24 weight % under condition.

The invention further relates to alkali silicate as the film for additive in manufacture closed-cell foam with the foam The purposes of film is formed in the closed pore of body.

The invention further relates to a kind of method for manufacturing closed-cell foam product, methods described includes providing a kind of composition, institute State and the alkali metal silicate that a kind of composition is included in offer sufficient amount in the resin compound of curable formation closed pore product is provided Salt in the closed pore of foams to form film.

It is worth noting that, for the sake of clarity, some features of the invention described in different embodiments Offer can also be provided in single embodiment.On the contrary, for simplicity, this hair described in single embodiment Bright various features can also be provided separately or be provided with any appropriate sub-portfolio.

It is described for illustrating when using word "comprises/comprising" and word " have/including " in the present invention The presence of feature, integer, step or component, but do not exclude the presence of or add one or more further features, integer, step, Component or combinations thereof.

Brief description of the drawings

According to the description (being only used for illustrating) of embodiments below, and this will be more clearly understood in the accompanying drawing with reference to appended by Invention, the accompanying drawing is the scanning electron microscope diagram of various phenolic foam samples described herein.SEM (SEM) technology of preparing of sample is described in annex 1.

Fig. 1 is the scanning electron microscope diagram of the foams of comparative example 1, and it shows the pore structure tool of high water phenolic foams There are many pinpricks.Phenolic resin, foaming agent and the acid catalyst of the preparation do not include alkali silicate, and the total water having contains Measure as 19.05%.

Fig. 2 is the scanning electron microscope diagram of embodiment 1, and it shows silica dioxide gel covering pinprick, although adding more Phenolic resin, foaming agent and the acid catalyst of high water content 21.85%, but with sodium metasilicate come protection hole.

Fig. 3 be comparative example 1 foams scanning electron microscopy, the poroid pinprick of its display of high resolution.

Fig. 4 is the scanning electron microscope diagram of the foams of embodiment 3, and the silica dioxide gel of its display of high resolution covers The poroid pinprick of lid.

Embodiment

It should be noted that with some commercial resins of existing surfactant formulatory.

The preparation of Resin A：

Based on weight, pass through phenol, 3.05 parts of water and 1.07 parts of 50% hydrogen of 57.8 parts of the mixing that flowed back at 20 DEG C Potassium oxide prepares Resin A.Temperature is increased to 74-76 DEG C and 91% paraformaldehyde for adding 30.4 parts through 2 hours.Then will Temperature is increased to 80-82 DEG C and maintained until viscosity reaches 6500cP.Begin to cool down and simultaneously the water of 3.3 parts of addition, 4.1 parts Diethylene glycol and 3.6 parts of ethoxylated castor oil (surfactant).Final resin contain 17% water and as plasticizer 4 Weight % diethylene glycol.The resin contains 8% free phenol and free formaldehyde less than 2%.Viscosity at 25 DEG C is 2500-3500cP。

The preparation (distillation Resin A) of resin B

Based on weight, pass through phenol, 3.05 parts of water and 1.07 parts of 50% hydrogen of 57.8 parts of the mixing that flowed back at 20 DEG C Potassium oxide prepares resin B.Temperature is increased to 74-76 DEG C and 91% paraformaldehyde for adding 30.4 parts through 2 hours.By temperature liter Up to 80-82 DEG C simultaneously maintained until viscosity is 6500cP.Begin to cool down to 60 DEG C and 4.1 parts of diethylene glycol of addition simultaneously.Very Sky distills out 3.3 parts of water, continues cool to 40 DEG C, then adds 3.6 parts of ethoxylated castor oil (surfactant).Most Whole resin contains 11.5 weight % water and the 4.2 weight % as plasticizer diethylene glycol.The resin contains 7.3% Free-phenol and 1.1% free formaldehyde.Viscosity at 25 DEG C is 7950-9000cP.

Embodiment prepared by foams

All results are shown in Tables 1 and 2.

Embodiment 1-9 in table 1 is all formulations including alkali silicate.Comparative example 1 is same as Example 1 to be removed Comparative example 1 does not include outside silicate.Comparative example 9 is same as Example 9 in addition to comparative example 9 does not include silicate.

When preparing the foam sample of laboratory scale in the following Examples and Comparative Examples, all chemicals additions are equal It is (21 DEG C) progress at room temperature, unless otherwise indicated.

Embodiment in table 1, which is shown, works as the formulated phenolic resin mixture for including surfactant, acid and foaming agent not When total water content in the case of the filler for considering to be optionally present is more than 15% but is less than 24%, as long as by resin compound system The alkali silicate of 1-10 weight % debita spissitudo in the foams obtained also be present, be just made and show to manage after heat ageing The foams of the lower thermal conductivity of the stabilization for the aged thermal conductivity's value thought.

Even if the embodiment in table 2 shows the alkali silicate of the appropriate amount for the 1-10 weight % that foams be present, if The water content of formulated phenolic resin system is more than about 24%, then the thermal conductivity after heat ageing is higher than 0.025W/m.K.If setting Water content in resin system is too high, and the intensity of foams may not be large enough to that there is enough structural intergrities to allow to Support oneself, and may cave in.This foams to cave in are undesirable.Embodiment 1 in table 1 is identical shown in table 1 Formulation.Total water that comparative example 2-4 is shown in increase resin compound before activated resin mixture forms froth pulp contains The influence of amount.Comparative example 4 produces the foams to cave in, therefore is not suitable for use in foam heat-insulating product.The foams of comparative example 4 collapse Collapse is because high water content.Comparative example 5 reappears GB 135476 experimental work, and it shows that foams have very high thermal conductivity Rate is not appropriate for as modern insulation material.

In all embodiments and comparative example shown by Tables 1 and 2, acid catalyst C is 65 weight % with 4: 1 weight Than aqueous phenolsulfonic acid/phosphoric acid of mixing.Foaming agent E be 95 weight % 85/15 pentamethylene/isopentane and 5 weight % it is complete The mixture of fluothane hydrocarbon.Foaming agent F is isopropyl chloride/isopentane mixture of 60/40 weight.

It is the phenolic foams of the preparation laboratory scale used in embodiment 1-9 and comparative example 1-5 and 9 below Two methods.

The thermal conductivity of the total water content and alkali silicate and foam sample of preparing resin system is charged into the He of table 1 Table 2.

Embodiment 1-9 and comparative example 2-4：The bubble for adding alkali silicate to phenol-formaldehyde A or bakelite B and manufacturing Foam body, wherein being catalyzed foaming agent E or F by sour C

The solid of suitable concn is added in the Resin A of the parts by weight of forward direction 100 of sour addition or resin B phenolic resin or is contained Aqueous alkali metal silicate.

By the sour C of 20 parts by weight and with the pre-emulsified phenolic resin/silicate of foaming agent E or F of the parts by weight Mixture mixes.

Use highest 3000rpm mixed at high speed.Mixture obtained by 260g+/- 10g is added through 20 minutes at 70 DEG C Size is to solidify in 300mm × 300mm × 50mm photo frame mold and form the hard foam of 50mm thickness.Exist in an oven The foams are dried at 70 DEG C.Drying time is to solidify foam thickness per 10mm in 1 hour.

The plate foam body sample for preparing 300 × 300 × 50mm is used for measuring thermal conductivity.Use what is provided in EN1602 Method records density foam.

The compound heat flow appearance measurement initial lambda values of laser and aging λ value are used at 23 DEG C of mean temperature.According to European standard EN 13166：2008 (or EN 14314：2009) method is by one section of longer time of foams heat ageing (in this case 110 2 weeks at DEG C).

Comparative example 1 and 9：The foams for adding alkali silicate not into phenol-formaldehyde A and manufacturing, wherein being urged with sour C Change foaming agent E or F

By the sour C of 20 parts by weight with the Resin A of pre-emulsified 100 parts by weight of foaming agent E or F of the parts by weight Phenolic resin mixes.

Ibid, the plate foam body sample for preparing 300 × 300 × 50mm is used for measuring thermal conductivity.According in EN 1602 The method record density foam provided.

When by the embodiment 1-9 in table 1 compared with comparative example 1 and 9, it was demonstrated that add be based on first rank in the composition The alkali silicate of the 1-5 parts by weight of section phenolic resin produces lower thermal conductivity (λ), and wherein foaming mixture is not considering Total water percentage composition in the case of the filler being optionally present is 15-24%.

Table 2 reappears GB 1,351 476 embodiment, and the content of alkali silicate is based on first stage phenol in comparative example 5 Urea formaldehyde, acid and foaming agent but the not weight including vermiculite filler are 4.69%.The percentage composition of water is 37.28%, and this is to low The foams of thermal conductivity are very unfavorable.Therefore the GB 1,351 476 of the sodium metasilicate with similar dosage foam system is not made There must be the foams for stablizing lower thermal conductivity.Uncured composition is pulpous state, or even is not also formed in foaming and solidification suitable Close and form the foam production for example for cystosepiment, foam panels or c- sections with preferable hole-closing structure and enough hardness The phenolic foams of product.Therefore its physical property is so that it can not as viable material.Preferable physical property is made it have, There can not be preferable thermal conductivity.

Comparative example 2,3 contains such as the similar alkali metal silicate salt content used in GB 1351476 with 4, but has The advantage of the water percentage composition lower than GB 1351476.But comparative example 2,3 and 4 still can not obtain stabilization when aging Lower thermal conductivity (this is the purpose of the invention to be realized and aged thermal conductivity ＜ 0.025W/m.K.).

The invention is not restricted to embodiment as described above, and it can be changed in detail.

Annex 1

The preparation of SEM sample

One piece of 20mm × 10mm phenolic foams is cut from sample.The surface of the block phenolic foams is trimmed with blade To about 8 square millimeters.Then foams are broken along foam ascent direction record book in accordion form to expose clean surface.Remove the sample It is most of to leave 1mm foams thin slice in ascent direction.

Some Small loss of foam cell may be caused to produce surface to be checked by fractureing foam sample by hand.

The foams thin slice is fixed on aluminum steel sample using two-sided conductive viscous label.

Then the thin-layer coating of gold/palladium is carried out to sample (or multiple samples) using Biorad SC500 ion sputtering instruments (about 2.5 angstroms).The reason for coated sample is that (a) increase conductive surface is stronger to take away electric charge and (b) raising density acquisition Imaging.In our current research under involved magnifying power, the influence of coating is negligible.

Sample imaging is carried out under the following conditions using FEI XL30ESEM FEG SEM：10kW accelerates electricity Pressure, operating distance is about 10mm.Detected under × 1200 to × 20000 magnifying power.Different magnifying powers make pore-size distribution and Defect is presented in foam hole.

The SEM (SEM) of embodiment 1, embodiment 3 and comparative example 1 is illustrated in Fig. 1-4.

SEM 1 (Fig. 1) and SEM 3 (Fig. 3)-these figures show that phenolic foams obtained in comparative example 1.In hole It can be seen that many pinpricks on wall.

SEM 2 (Fig. 2)-the figure illustrates the phenolic foams of embodiment 1.Pinprick on hole wall seem it is less and by Covered in the addition major part of sodium metasilicate by film, this is attributable to the formation of silica dioxide gel.

SEM 4 (Fig. 4) shows the embodiment 3 with 4.4 parts of sodium metasilicate pentahydrates.Pinprick on hole wall is most of Covered by film, this is attributable to the formation of silica dioxide gel.

Claims

1. phenolic foams, it includes phenolic resin, hydrocarbon blowing agent and with existing at least 1 weight % amount of the foams Alkali silicate, wherein the foams are formed by phenolic resin blend, the water content of the phenolic resin blend is 12 weight %-24 weight % of the resin compound, according to EN 13166:2008 or EN 14314:2009 method measures institute The aged thermal conductivity for stating foams is less than 0.025W/mK.

2. the foams described in claim 1, wherein the foams are formed by phenolic resin blend, the phenolic resin mixes The water content of compound is 15 weight %-24 weight % of the resin compound.

3. the foams described in claim 1 or 2, wherein the alkali silicate is with 1 weight %- of the phenolic foams 10 weight % amount is present.

4. the foams described in claim 1 or 2, wherein the alkali silicate is with 2.5 weights of the phenolic foams The amount for measuring %-5 weight % is present.

5. the foams described in claim 1 or 2, wherein the alkali silicate is hydration, and formula is A₂SiO₃· nH₂O, wherein A are the alkali metal of the 1st main group of the periodic table of elements, and n is 1-9 integer.

6. the foams described in claim 1 or 2, wherein the alkali silicate is selected from sodium metasilicate, potassium silicate and lithium metasilicate In one or more.

7. the foams described in claim 1 or 2, wherein the silicate is sodium metasilicate pentahydrate.

8. the foams described in claim 1 or 2, wherein the silicate is potassium silicate.

9. the foams described in claim 1 or 2, wherein the silicate is lithium metasilicate.

10. the foams described in claim 1 or 2, wherein the hydrocarbon blowing agent includes at least one pentane.

11. the foams described in claim 10, wherein the hydrocarbon blowing agent includes the mixture of pentamethylene and isopentane.

12. the foams described in claim 10, wherein the hydrocarbon blowing agent includes the mixture of isopropyl chloride and isopentane.

13. the foams described in claim 1 or 2, wherein the hydrocarbon blowing agent includes perfluoro alkane.

14. the foams described in claim 1 or 2, wherein the foams are formed by resol mixture, it is described The water content of resol mixture is more than 15 weight % but is less than 24 weight %, and the alkali silicate with At least 1 weight % of foams amount is present.

15. the foams described in claim 14, wherein the alkali silicate is with described in the case where not considering filler 1 weight %-10 weight % of foams amount is present in the resol mixture.

16. the foams described in claim 15, wherein the alkali silicate is with described in the case where not considering filler 2.5 weight %-5 weight % of foams amount is present in the resol mixture.

17. manufacturing the method for froth pulp, methods described includes forming foams by composition to manufacture closed-cell foam product, institute Stating composition includes：

The phenolic resin of surfactant, catalyst, foaming agent and alkali silicate is included, and

The filler being optionally present,

The water content that the composition has in the case of the filler for not considering to be optionally present is 12 weight %-24 of composition Weight %,

According to EN 13166:2008 or EN 14314:The aged thermal conductivity that 2009 method measures the closed-cell foam product is small In 0.025W/mK.

18. alkali silicate is used for the use for manufacturing closed-cell foam product as the additive in phenol formaldehyde foam resin combination On the way, wherein the water content of the phenol formaldehyde foam resin combination, in the case of the filler for not considering to be optionally present, for the combination 12 weight %-24 weight % of thing, according to EN 13166:2008 method measures the aged thermal conductivity of the closed-cell foam product Less than 0.025W/mK.

19. alkali silicate is used to be formed in the closed pore of foams in the production of closed-cell foam as film for additive The purposes of film, wherein the foams are formed by phenolic resin blend, the water content of the phenolic resin blend is should 12 weight %-24 weight % of resin compound, according to EN 13166:2008 or EN 14314:2009 method measures described The aged thermal conductivity of foams is less than 0.025W/mK.